Process for sweetening hydrocarbon oil



May 26, 1936. c. o. HOOVER 2,042,054

PROCESS FOR SWEETENING HYDROCARBON OIL Filed Nov. 11, 1950' 3 Sheets-Sheet l A TTORNEYJI May 26, 1936. c. o. HOOVER PROCESS FOR SWEETENI NG HYDROCARBON OIL Filed Nov. 11, 1930 3 Sheets-Sheet 2 y 1936- c. o. HOOVIEIIQ 2,042,054

PROCESS FOR SWEETENING HYDROCARBON OIL Filed Nov. 11, 1930 5 Sheets-Sheet 3 unllna 60 a a @M? A TTORNEYJ.

R INVENTOR.

Q fiZaue/n Patented May 26.19 a I 2,042,054

UNITED STATES PATENT :OFFICE rnocEss roa SWEETENING mam cannon on.

Charles 0. Hoover, San Antonio, Tex., assignor v to Bennett-Clark 00., Inc., San Antonio, Tom, a corporation of Texas Application November 11, 1930, Serial No. 494,913

'1 Claims. (01. 196-29) The present invention relates to the purificatreated oil from tank I is passed by pipe line 2 tion of mineral oil materials and particularly through pump 3 and pipe line 4 into an aspirathe relatively light mineral oil distillates such as tor device which constitutes a mixing chamber v gasolene, kerosene and the like, for removing or designated as 6, and in which the oil is mixed 5 altering "sour compounds" namely, compounds, with dry pulverulent chemicals from the hop--v 5 which contain sulphur, including organic sulphur per or supply tanki. The oil then passes through compounds such as mercaptans and also free sulpipe 1 into one or more filter presses '8, the filtered phur and hydrogen sulphide, as well as any oroil passing out through pipe .9 into storage tank ganic sulphur compounds which may have been l0. v

formed in the oil by treatmentwith sulphuric acid In referring to the oil in tankl as untreated 10 or sulphur dioxide or other acid compounds conthis does not mean that the oil at this stage must taining sulphur with which the oils or distillates not have .undergoneany treatment whatsoever; have been treated. In fact the oil preferably hasbeendistilled and The process is especially important in the case may also have been treated with sulphuric acid is of treating gasolene and similar light fractions, or similar reagent, by any desired or approvedw produced from oils containing relatively large method. During the first'part ofthe p'rocessthe amounts of sulphur compounds existing in the pulverulent material will be introduced from hopform of organic sulphur compounds. per 5 into the mixing chamber 6,until the leaves An object of the present invention is to pro-' of the filter press have accumulated. a sufficiently vide a highly efiicient solid chemical, in a finely dense and thick coating, to act as a filter. This 20 divided state, capable of reacting with the sulcoating on the leaves of the pressmay be from phur compound in the oil. A further object or half an inch up to two inches or even more inches the invention is the provision of novel modes of in thickness, depending upon the amount and, applying finely divided solid reagents to the treatcharacter of the impuriti s in 8911 n r a ment and purification of mineral oil distillates. ment. When such a sufficient quantity or mate- 25 In the accompanying drawings I have shown rial has been deposited upon the leaves of the diagrammatically certain kinds of apparatus filter press, the outlet of the hopper 5 is closedwhich may be used in carrying out thetreatment, which prevents the introduction of further but it is to be understood that the invention is in quantities ofthe' purifyin chemical into the oil no sense restricted to these particular types of u der treatment The P p 3 15 Of a n -go apparatus. capacity to buildup any desired amount of pres- Figure 1 shows a diagrammatic view of one 'sure in the pipe line 7 andin the intake side or modification of the process in'which the filter the filter press. The, amount of pressure can press, or a series of filter presses constitute the e Va e between W e i s, Say f om 5 01 10 essential treating element. pounds up to 100pounds, of course a sumcient Figure 2 shows a system of apparatus in which amount. of pressure is employed to drive the the treatment is largely effected in contact or setoil through the cakes of filtering material detling chambers, these being preferably provided posited on the leaves ofthe filter press.

with conical bottoms in order that there will be a Having built up a substantial cake of the puri- 40 considerable amount of agitation of the distilfying chemical upon each of the leaves of thefilter 4Q lates in the bottom of the treating tank, while press, as shown for example inFigure 4 of the the upper portion of the tank is of larger diamdrawings, the distillate can be passed through this eter so as to allow the chemical to settleout cake or layer for a considerable time, and the from the oil after it has been well contacted chemical contained in the cake .will treatthe therewith in the lower part of the tank. oil or distillate by reaction with the sulphur com- 5 Figure 3 shows a convenient arrangement of pounds therein. After a time the filtration may several filter presses, whereby the oil may be be found to be only partially successful inremovpassed through a number of the presses in any ing the sulphur compounds, andwhen thisstage desired sequence, and whereby the filter press has been-reached the distillate may pass froma or presses which havebecome completely fouled first filter" press into and through a second filter 50 by the removal of impurities from the oil can be press already provided with cakes of the purifying cut out temporarily for recharging. agent, The apparatus can be runin this condi- Referring more particularly to Figure 1, which tion until it is found that the cakes of the material constitutes the showing of the apparatus for the in the first-filter press are practically inactive,

preferred modification of the process, the unand are removing or altering practically no sul-. 55

phur compounds. Then this first filter pres can be cut out of the system and the distillate can passdirectlyto thesecondfilterpresawhilethe first press will be recharged with fresh filteringhyroxide may be used. Salts or hydroxides or' oxides of other metals such as iron, zinc, lead, mercury, aluminum, cadmium and other metals may be employed, or mixtures of these. These compounds and salts may be generally characterized or described as compounds and salts which react with mercaptans to form mercaptides. Also metals may be employed with the salts, for example, metallic iron may be used with copper chloride. Copper sulphide in admixture with an adsorbent material such as absorbent or adsorbent clay may also be employed in sweetening sour hydrocarbon oil.

Very satisfactory results may be produced by mixing clay with an equal amount of copper chloride, and grinding the mixture in a ball mill until it passes through a 200 mesh screen, or until most of it passes through such a screen and the entire material would pass through a 100 mesh screen. This may be then mixed with a considerable amount of additional clay of about the same degree of fineness. either in the ball mill or in any other suitable manner.

In many cases it is also advisable to employ a highly oxidizing salt, and for this purpose I may mix potassium permanganate or potassium manganate with clay and reduce this mixture to the fine state above referred to, and then add this to the mixture of clay and copper chloride. Very satisfactory results are produced by using a reagent containing say 90% of dry clay, 5% of cupric chloride and 5% of potassium permanganate.

The oxidizing salt may be omitted in some cases, for example, where the sulphur content is quite low and where no elementary sulphur is present in the oil. with oils containing elemental sulphur, for example, with gasolene containing elemental sulphur or with gasolenes which are high in total sulphur, and with the heavier distillates such as kerosene, naphtha and the like, or with pressure distillates whether or not they contain elemental sulphur and whether or not they are high in sulphur, it is advisable to employ the oxidizing salt.

A particular advantage of the form of apparatus shown in Figure 1 is that the oil and the clay are not in contact with each other for a long period. The continued contact of clay with gasolene, and particularly with the cracked gasolenes or gasolenes containing a large amount of unsaturated compounds is well known to produce gums by polymerization of the unsaturated compounds. In my process the time of contact of the oil with the clay is very short and the formation of gum is avoided and the amount of gum in the 'gasolene may be substantially reduced, perhaps by absorption of the same in the clay.

In many cases, gasolene, kerosene, naphtha and the like, may be improved simply by filtrafl n. by

have been subjected to sodium 'plumbite or doctor solution, and from which, as leadisordinarilyprecipitatedbyaddingasmall amount of free sulphur. I find that it is entirely pomible to wholly eliminate the addition ofiree sulphuhortoaddwhatwouldbeconsideredin the prior practice a wholly insufiicient amount 10 of free sulphur, and then filter the gasolene throughthefilterpresses-containingabedof clay on the leaves of the press. By this method the lead mercaptidesseemtobeatleastpartly removed. Thetreatmentalsodoesnotproduoe ll snygumintheoilor doesnot leave a'gasoline :lgch has a high tendency to form gum on stand- In the ordinary treatment of gasoline, for example,inthesystemillustratedinl"igurelof$0 the drawings, if the gasolinehas been treated with sulphuric acid, according to any of the standard procedures, I find it is inadvisable to wash the gasoline or otherwise attempt to remove alloftheremaining Thegasolinestillcon- 25 tainingsomesoacanbepassedthroughthesystem as here illustrated, and will come out of the filter press entirely neutral. In the treatment of gasoline which has not been subjected to sulphuric acid treatment, if the mercaptan content of the oil is rather high, for example. in pressure still distillates, I would recommend adding asmall amount otsulphur dioxide, for example, half a per cent or less, through the pipe ll. Hydrogen sulphide could be added in a similar mannler and in about the same percentage or less. Other acids, for example, hydrochloric acid gas could be similarly introduced this being in small amount, say a quarter of a per cent or is. Even when adding such acids the gasoline comes 4 out of the filter press entirely neutral. This step is of material help in the treatment of gasolines which are rather dark in color, and the color of the filtered gasoline will be toimd to be very much improved by the treatment. This step is of material help in the case of oils which contain elementary sulphur in solution, aiding in removing the same.

Referring now more particularly to Figure 2 of the drawings this shows a modified mode of treating oil with the above mentioned reagents. The distillate comes from the tank I through pipe 2, pump 3, pipe 4, mixing chamber 8 and pipe I as in the modification shown in Figure 1. The mixture of oil and reagent passes into the 55 lower end oi a hoppered vertical tank I, being introduced as shown in an upward direction. The settling reagent tends to collect in the lower end of the tank, by gravity, and the incoming oil stirs this up and mixes the said reagent with the oil. The upper part of the tank is of larger diameter and by the timethe oil reaches the upp part of this tank the major quantity of the reagent will have settled out so that clear oil will flow through pipe ll into a similar tank i5. Any

small amount of reagent carried through pipe M will tend to settle in the lower part of tank II, and if desired, a slow stream of oil can be continuously through pipe l8, pump l1 and pipe l8 back into the first treating chamber It. The 70 pump II can be run continuously or intermittently as desired. Th oil leaves the upper part of tank l5 by pipe i8,ispassed through thefilter press 20, pipe line 2| into storage tank 22. If desired, a pump may be introduced in pipe line ll. 7

The plates of the filter press Zlhmay be and preferably are, preliminarily coated with clay or with a mixture of the clay and chemicals as described above, as a preliminary operation. This mode of treatment maybe advisable in plantswhich are already equipped with hopper bottom storage tanks or treating tanks, but I prefer the apparatus as shown in Figure 1.

As stated above the filter press method is far superior to the treating tank method. Not only is the apparatus greately simplified and made less expensive, but since clay and the chemicals are of substantially different specific gravities, there is considerable tendency for the chemicals to separate out from the clay in the tall treatis no opporamount of the gasoline can be sweetened by the use of a small quantity of the reagent. For example, gasoline from Winkler crude (West Texas) which is extremely high in sulphur, I have treated in the ratio of. over 5,000 gallons of the gasoline with one pound of copper chloride. With such a gasoline however I would prefer to also employ the permanganate, in order to improve the color.

I have referred above, in the manufacture of the reagent, to grinding the clay and copper chloride in a ball mill. Another mode of operation would be to impregnate the clay with copper chloride solution, and then dry this at a relatively low temperature so as not to decompose the copper chloride. Another suitable method would be to grind the clay and copper chloride or potassium permanganate or manganate, in a somewhat moist condition, for example, containing 25 to 30% of water. This will produce a mixture which would be too moist, but the moisture content of this can be reduced, for example, by adding well dried clay to the mixture in the ball mill, for diluting the reagent down to the preferred of copper chloride.

I have referred to the removal or alteration of sulphur in the sour oils. In order to get rid of the sourness, it is not necessary that the sulphur be wholly removed (1. e. taken out of the oil) if it is so changed that the oil will stand the doctor test, i. e. treatmentwith sodium plumbitesolution, without giving a brown or black color.

Figure 5 is one form of mixer which can be 5 used at 6 (Figures 1 and 2) When using a series of filter presses, as shown in Figure 3, I would coat the leaves of each of the presses, say at the beginning of the run, and the leaves of each press are of course coated by the method described-above, before that press is used.

I claim:

1. The process for sweetening sour hydrocarbon oil which comprises contacting same with a mixture comprising adsorbent clay, cupric chloride and a permanganate.

2. The process for sweetening sour hydrocarbon oil distillates which comprises contacting same with a mixture comprising an absorbent earth, a compound reacting with mercaptans to form mercaptides, and a strongly oxidizing manganese compound.

.3. The process for sweetening sour hydrocarbon oil distillates which comprises contacting same with a mixture comprising pulverized absorbent earth, a compound of a metal readily reactable with mercaptans to form mercaptides, and a strongly-oxidizing manganese compound.

4. The process for sweetening sour hydrocarbon oil which comprises contacting same with a mixture comprising cupric chloride and an adsorbent material in the presence of an oxidizing manganese compound.

5.'The process for sweetening sour hydrocarbon oil which comprises contacting same, in the presence of an oxidizing manganese compound, with a mixture comprising an adsorbent material and a compound which reacts with mercaptans to form mercaptides.

6. The process for sweetening sour hydrocarbon oil which comprises contacting same, in the presence of an alkali permanganate, with a mixture comprising an adsorbent material and a salt which reacts with mercaptans to form mer- 45 captides.

7. The process for sweetening sour hydrocarbon oil which comprises contacting same, in the presence of a permanganate, with a mixture comprising an adsorbent material and cupric 50 chloride.

CHARLES O. HOOVER. 

